Dyeing, printing, or stenciling of materials made of or containing cellulose derivatives



Patented June 20, 1933 UNITED STATESOPAQTENT oFFrcE HENRY DREYFUS, on noNDoN, AND GEORGE HOLLAND ELLIS, roams ocxnmN AND HENRY CHARLES OLPIN, OF SPONDON, NEAR DERBY, ENGLAND, ASSIGNOBS TO CED SE CORPORATION OF AMERICA, A CORPORATION OF DELAWARE DYEING, PRINTING, on s'rENcILme or m'rnams MADE or on. coN'rAINING "CELLULOSE DERIVATIVES No Drawing. Application filed April 19, 1929, Serial No. 356,601, and in Great Britain ,April 26; 1928.

This application, which is a continuation in part of U. S. application Serial No. 162,938 filed 22nd January, 1927, relates to the dyeing, printing, stenciling or otherwise colouring of threads, yarns, knitted or woven fabrics or other products'made of or containing cellulose acetate or other organic acid esters of cellulose, such for example as celluloseformate, propionate, or butyrate, or the prod-- ucts obtained by the treatment of alkalized cellulose with estei ifying agents g. the product known as immunized cotton), or made of or containing cellulose ethers, such as methyl, ethyl, or. benzyl cellulose, or the corresponding condensation products of cellulose and glycols or other polyhydric alco hols, allof which cellulose derivatives aretiofi derivatives of-cellulose.

U. S. application S. No. 162,938 describes and claims, inter, alia, the dyeing or otherhereinafter referred to as organic substitu- I wise colouring of thesaid organic substitution derivatives-of cellulose by means of dyestuffs or compounds containing one or more urea or thiourea residues. In the course of further researches we have found that especially useful results are obtained by dyeing or otherwise colouring the cellulose acetate or other organic substitution derivatives of cellulose with particular unsulphonated colouring matters or compounds of this class which are azo dyes obtainable by coupling diazotized amino-substituted symmetrical diarylureasor diarylthioureas with azo coupling components.

' or alkyl, alkyloxy, amino, or acidyl-amino groups. The dyeing or colouring with the azo dyes may be effecteddirectly or by producing the azo dye within the cellulose derivative, for example, by treating the materlal firstv with the amino compound, then with 1161. The following table shows the shades given The aryl groups may contain further substituents such as halogen,

by some colouring matters which may be used according to the invention,

Colouring matter. I Shade.

Pure yellow Golden orange Yellow Yellow Greenlsh-yellow Orange yellow Yellow The colouring matters or compounds may be applied in aqueous solution (when sufficiently'soluble), or in aqueous suspensions gr colloidal solutions or-dispersions obtained water contaming or notcontaining protec tive colloids ordis'persators, by pretreating the colouring matters or compounds with disj per-sing agents or .by other methods. Of the dispersing agents whichare suitable for obtammg such dispersions maybe mentioned grinding-1 (forexample in colloid mills), by dissolving ina solvent and pouring into those described in U. S; Patent Specifications I Nos. 1,618,413, -,1,c1s,414 and 1,694,412 and British Patents Nos. 273,819 and 273,820; viz.

bodies of oily or fattybharacteristics, namely a higher. fatty acids orsulphonated or other derivatives thereof containing salt-forming groups, such as sulphoricinoleic acid or'other sulphonated fatty acids or salts of such acids or bodies, for instance their alkali orammonium salts, used aloneor in conjunction with auxiliary solvents as described in U. S. Patent Specification No. 1,690,481 and British Patent N 0. 269,960; carbocyclic compounds containing in their structure one or" moresalt forminggroups or salts of such compounds;' sulpho-aromatic fatty acids or salts thereof; Y sodium or other soluble salts of resin' acids.

LMixed goods containing for example, in addition to the organicsubstitution derivative or derivatives of cellulose, cotton, silk, wool, or the cellulose other fibres or threads, may be dyed or othertype of artificial silk or and soluble resin soaps or .0 phenylurea with 2 molecular proportions of in association,

wise coloured with or without employment of other dyestuffs or components according to the character of the-threads or fibres used such other dyestufls or com onents being applied if desired either beore or after the application of the colouring matters or compounds of the present invenphenol are well stirred into 300-400 grams of the sulphoaromatic fatty acid product pre= processed with risin to the pared according to Example 'A of U. S. atent Specification No. 1,694,413. The mixture is heated until the maximum degree of dispersion is achieved, and then diluted with boiling water and added through 'afilter cloth to 300 litres of water contained in avsuitable dyeing machine. The goods are entered and common met ods of dyeing until'the shade is achieved. They are now lifted,

rinsed, and dried or-otherwise treated as uisite.

. y replacing the cellulose acetate fabric in this example by, a cellulose formate fabric the latter is likewise dyed in yellow shades.

' Ecmaple 2 To dye 10, kilos of cotton cellulose acetate 50), the cotton a blue shade, and

t e cellulose acetate golden orange.

The cotton portion of the goods is first dyed with Duranthrene blue G. C. D. (Colour Index No. 1113) by the method detailed in Example 20f U. S. application Serial No.

83,138 filed 22nd January, 1926, and the unilyed .celluloseacetate then covered as folows:--

250 grams of 25% aqueous paste, of the dyestufi' obtained by coupling 1 molecular proportion of tetrazotized 4:4='-diamno-diphenylurea with 2 molecular proportions of Im-phe'nylene-diamine are well stirred with y 250 cos. of turkey red oil (50%) the mixture is heated with an open steam pipe, diluted with water, and further boiled. The dyebath' is t en made up, the fabric-entered,

land dyeing. carried out as in=Example 1 above, the goods being afterwards lifted,

rinsed, and dried,-or otherwise treated .as

I 1 at-we claim and desire to secure by Letters Patent is:-'- 1 temperatures according 1. Process for dyeing materials comprising organic substitution derivatives of cellulose which comprises dyeingthem with unsulphonated azo colouring matters of the general formula wherein X represents oxygen or sulphur, and R and R represent aryl or substituted aryl residues at least one of which is of the type RN=N-R B being an aryl residue and R the residue of a coupling component.

2. Process for dyeing materials comprising organic substitution derivatives of cellulose which comprises dyeing them by forming thereon unsulphonated azo" colouring matters of the general formula R.-NHoxN1iwherein X represents oxygen or sulphur,

and R and R represent aryl or substituted aryl residues at least one of which is of the type -RN=NR B being an aryl residue and R the residue of a coupling component. 4

3. Process, for dyeing materials comprising organic substitution derivatives of cellulose which comprises dyeing them with diazotizable unsulphonated azo colouring matters of the general formula wherein X represents oxygen or sulphur, and R and R represent a 'l or substituted aryl residues at least one 0 which is of the a type RN=NR B being an aryl residue and R the residue of a coupling component, and diazotizing anddeveloping with an azo coupling component.

1. Process for dyeing materials comprising cellulose acetate which comprises dyeing them'with unsulphonated azo colouring matters of the general formula wherein X represents oxygen or sulphur, and R and R represent aryl or" substituted aryl residues at least one of which is of the type :RN=N-R,, B being an aryl residue and R the residue .of a coupling component.

5. Process for dyeing materials compris ing cellulose acetate which comprises dyeing them by forming thereon unsulphonated azo colouring matters of the general formula wherein X represents oxygen or sulphur, and B and R represent aryl or substituted aryl residues at least one of which is of the type -RN=N-R,, B being an aryl residue and R, the residue of a coupling component.

t. 6. Process for dyeing materials comprismg cellulose acetate which comprises dyeing them with diaz'otizable unsulphonated azo colouring matters of the general formula.

Ih-NH-CX-NH-R wherein, X represents oxygen or sulphur,' gr

and R and R represent aryl or substituted aryl residues at least one of which is of the due andrR the residue of a coupling component, and diazotizing and developing with an azo coupling component.

7. vProcess for dyeing materials comprising cellulose acetate which comprises dyeing them with aqueous colloidal dispersions of unsulphonated azo colouring matters of the general formula wherein X represents oxygen or sulphur, and R land R represent aryl or substituted aryl residues at least one of which is of the type -R-N=N-R R beingvan arylresidue and R the residue of a coupling component. t r

8. Materials comprising organic substitup tion derivatives of'cellulose dyed with un-' -R {NHCXNH-R wherein X represents oxygen or sulphur,

and R and R represent aryl or substituted aryl residues at least one of which is of the due and R the residue of a coupling component. 10. Process for dyeing materials comprising organic substitution derivatives of cellulose which comprises applying thereto azo coloring matters free from'sulp onic groups and obtainable diazotizing and couplin with coupling components compounds of the general formula NH .CX.NH in which X represents oxygen or sulphur, symmetrlcally substituted in the NH groupsby two aryl v 4 groups at least one of which contains a diazotizable amino group.

11. Process for dyeing materlals comprising organic substitution derivatives of cellulose which comprises applym thereto azo coloring matters free from su phonic and ,carboxylic groups and obtamable by dlazo- ,tizing and coupling withcoupling compo nents compounds of the general formula NH .CX.NH in which Xrepresents oxygen or sulphur, symmetrically substituted in the NH groups by two aryl groups at least one 79 of whlch contains a diazotizable amino oup. r

12. Process fir dyeing materials compris ing organic substitution derivatives of cellulose which comprises applying thereto azo coloring matters free from sulphonic and carboxylic groups and obtainable by diazotlzing and coupling with coupling com ponents compounds of the general formula NH .GX.NH in which X represents oxygen 80 or sulphur, symmetrically substituted in the NIL groups by two phenylgroups'at least one of which contains a diazoti zable'amino group.'

13. Prdcess for dyeing materials comprising organic substitution derivatives ofcellulose which comprises applying thereto azo coloring matters free from sulphonic and carboxylic groups and obtainable by rdiazotizing and couplying with coupling components of the benzene seriescompounds of the general formula NH CXNH in which X represents oxygen or sulphur, symmetrically substituted in the NH groups by two aryl groups at least one of which oontains a diazotizable amino group.

14. Process for dyeing materials comprising organicsubstitution derivatives of cellulose which comprises applying thereto azo coloring matters free from sulphonic and car- 109 boxylic, groups and obtainable by diazotizing and coupling with coupling compo- 1 nents compounds of the general formula NH .CX.NH in which X represents oxygen or sulphur, symmetrically substituted in the 195 I NH groups bytwo phenyl groups at least one of which contains a diazotizable amino I group and at least one a, substituent selected from the group consisting of halogen, alkyl, alkoxy and acidylamino. no

15. Materials comprising-organic substitution derivatives of cellulose colored with v azo coloring matters free from sulphonic groups and obtainable, by diazotizing and coupling with coupling. components com- 1 pounds of the general formula NH .CX.NH in which X represents oxygen or sulphur, symmetrically substituted in the NH groups g by two aryl groups at leastone cgf which 1 contains a diazotizable amino grou 16''. Materials comprising organic substitution derivatives of cellulose colored with azo coloring matters free from sulphonic and carboxylic groups and obtainable by diazotizing and coupling with coupling components compounds of the general formula NH .CX.NH ,'in which X represents oxygen or sulphur, symmetrically substituted in the NH groupsby two aryl groups at least 13;

one of which contains a diazotizahle amino group. I

17. Materials com risin organic substi tution derivatives 0 cellu ose colored with azo coloring matters free from sulphonic and carboxylic groups and obtainable by diazo tizing and coupling with coupling components compounds of the general formula NH CXNH 'in which X represents oxygen or sulphur, symmetrically substituted in by two phenyl groups at the NH groups least one of which contains amino group.

18. Materials comprising organic substia diazotizable tution derivatives of cellulose colored with azo coloring matters tree from sulphonic and carboxylic groups and obtainable by diam-x tiZingand coupling with coupling componcnts of the benzene series compounds of the general formula NH .CX.NH,, in which X represents oxygen or sulphur, symmetrically substituted in the NH: groups by two aryl l' groups at least one of which contains a azotizable amino group. p

19. Materials com risin organic substitution derivatives'ocell ose colored with azo coloring matterslfree from sul honic and carboxylic groups and obtaina 1e by diazotizing and couphng with coupling components compounds of thegeneral formula NH .CX.NH in which X re resents oxygen or sulphur, symmetrically substituted in the NH, groups by two phenyl groups at least one of which contains a diazotizable amino group and at least one a substituent selected from the group consisting of halogen,-

alkyl, alkoxy and acidylamino.

In testimony whereof we have hereunto subscribed our names.

IENRY DREYFUS. GEORGE HOLLAND ELLIS. TOBIAS OCKMAN. v ,HENRY CHARLES OLPIN. 

